Linoleum and method of manufacturing



Patented Aug. 11, 1936 LINOLEUNI AND METHOD OF MANUFACTURING Robert D.Bonney, Glen Ridge, and Walter S.

Egge, West Orange, N. J., assignors to Congoleum-Nairn Inc., acorporation of New York No Drawing. Application June 30, 1934, SerialNo. 733,305

24 Claims.

The present invention relates to the manufacture of mouldablecompositions having a binder obtained from oxidized oil, saidcompositions including particularly linoleum and similar articles, and.more especially to an improved process of manufacturing suchcompositions and to the improved products resulting from such process.

Various types of compositions, generically termed linoleum weredeveloped and patented (United States Patent No. 87,277) by FrederickWalton over sixty years ago. His original linoleum compositions includedoxidized and solidified linseed oil, rosin, and kauri gum, speciallyprepared and fluxed together to form a binder or cement, this binderbeing then combined with pigments, wood flour, ground cork, and mineralfillers. It is characteristic of the compositions that they are plasticwhen freshly prepared and warm so that they may be rolled or pressedinto sheet form and subsequently or simultaneously united with a backingor supporting sheet and that, subsequent to forming into the desiredshape, they may be cured or seasoned by long continued exposure toheated air to the elastic firmness characteristic of the finishedproduct.

While many changes have since been made in the proportions of thematerials used in linoleum compositions, and Various additions andsubstitutions have been proposed, sometimes with a view to decreasingthe proportion of linseed oil and other costly constituents, andsometimes with a view to improving some quality of the product, theessential components of linoleum, its structure and physicalcharacteristics, and even the methods and equipment for producing it aretoday generically the same as they were sixty years ago. Particularly isthis true of the oxidized oil-resin-gum binder and it is to a majorchange in the character and composition of this component that ourinvention is primarily directed.

The linoleum binder is commonly called a cement by those skilled in theart. According to prior practice, all linoleum cements comprise anoxidized and solidified drying or semidrying oil, usually linseed oil,intimately fluxed with resinous material, usually rosin. There are twogeneral methods employed today for producing such cements. The older isthe two-stage method involving: (a) the oxidation and solidification ofthe linseed oil; and (b) the refluxing of the solidified oil with resinsand gums. The first step (a) may be accomplished by either of twoconventional methods: one, the Walton or scrim process; and the other,the Wood-Bedford or mechanically oxidized oil process. The Waltonprocess (British Patent No. 209 of 1860) consists in successivelyflooding vertically suspended cotton fabrics, called scrims, withlinseed oil which has been boiled with suitable driers,

each layer of oil being allowed to oxidize and coagulate or solidifybefore being followed by the the next flooding. The process isexceedingly slow, requiring from two to four months to produce a skin ofoxidized and solidified oil suitable for use. The Wood-Bedford method(British Patent No. 7,742 of 1893) on the other hand, is a rapidprocess, being completed in twelve to eighteen hours. It consistsessentially in aerating and agitating the linseed oil, together withsuitable driers, in a closed cylindrical vessel at a temperature ofapproximately 180 F., the aeration and agitation being continued untilthe oil is oxidized and solidified to the desired consistency. TheWood-Bedford method offers a great advantage in time saving, butunfortunately the solidified oil produced thereby is usually somewhatinferior to that produced by the scrim process. The second step (b) inthe two-stage method is the original, yet up-to-date, process 20described by Walton and consists in fiuxing, in a kettle of well knownconstruction, the solidified oil, produced in the first stage, withresinous material such as rosin, kauri gum, etc. The oxidized andsolidified oil produced by either the Walton or Wood-Bedford methodabove described may be used, but in order to produce a whollysatisfactory cement it has usually been found necessary to use at leasta substantial amount of the Walton or scrim process oil. The proportionof resinous material may vary from 20% to 35%, by weight, but generallysuch resinous material comprises a considerable proportion of rosin. Thefluxing is carried on at a temperature of 250 to 340 F. and underconditions substantially excluding air. The solidified oil, uponagitation with the rosin constituent of the resinous material, becomessomewhat mobile and in this state the several constituents of the cementmay be thoroughly and intimately mixed. Upon continued heating, however,the viscous mix commences to resolidify and such resolidification ispermitted to proceed until the mass is adjudged by the operator to be ofthe proper consistency for cement. It is then dumped into pans to cool.

The second method currently used for preparing linoleum cement is thesingle stage process developed by Ingle (British Patent No. 1,021 of1910). According to this method approximately three parts of linseed orother drying or semidrying oil, or mixtures thereof, and one part ofrosin or equivalent resinous material are placed in an oxidizer of theWood-Bedford type, the mix heated to a temperature of about 180 F. andaerated with constant agitation for a period of 14 to 24 hours. Duringthe treatment the oil becomes oxidized and partially solidified, theprocess being stopped and the mass dumped when the desired consistencyfor a good cement is obtained.

It is a fundamental characteristic of these previous methods ofmanufacturing linoleum cement that the oxidized oil from which thecement is prepared contains a substantial or major proportion ofcoagulated constituents (i. e. linoxyn) and is substantially oressentially solid at sometime before the preparation of the cement iscompleted. One method of chemically evaluating linoleum and linoleumcements consists in separating oxidized and solidified oil or cementinto three components, namely, Fraction I, that component which iscoagulated and is insoluble in.

ethyl ether and which is known as linoxyn and comprises coagulatedoxidized glycerides of linolic and linolenic acids; Fraction II, thatcomponent soluble in ethyl ether but insoluble in petroleum ether,comprising chiefly the oxidized but uncoagulated linolic and linolenicglycerides of the drying oil and capable of hardening without furthersubstantial oxidation; and Fraction III, that component soluble inpetroleum ether, comprising chiefly the unoxidized and non-hardeningconstituents of the oxidized drying oil, including unoxidized glyceridesof linolic and linolenic acids, unoxidizable and non-hardeningglycerides of saturated fatty acids, and oxidized but nonhardeningglycerides such as oxidized glycerides of oleic acid. The termnon-hardening is employed herein to indicate the property of retainingfluidity, even under the action of air, for long periods.

It is a fundamental characteristic of all linoleum cements heretoforeproduced or known that each comprises not only linoxyn but also allother constituents of the oxidized oil in substantially the proportionsin which they naturally occur in the oxidized oil. Thus, it is afundamental characteristic of all the linoleum cements heretoforeproduced or known that each comprises a substantial proportion oflinoxyn, i. e., Fraction I. On the basis of the total oil content of thecement, the percentage of linoxyn may vary from 30% to 55%, by Weight.Similarly, it is characteristic of all linoleum cements heretoforeproduced or known that each comprises a substantial percentage ofunoxidized and nonhardening constituents of the oxidized oil, i. e.,Fraction III. These constituents of Fraction III may vary from 15% to40%, by weight, on the basis of the total oil component of the cement.As a result, the proportion of the oxidized but uncoagulated glyceridesof linolic and linolenic acids, 1. e., Fraction II, will vary from 25%to 45% by weight. The definite and substantial proportion of linoxynpresent in all linoleum cements is required to offset or overcome thefluidity imparted to the cement by the presence of the likewisesubstantial amount of unoxidized and nonhardening oil constituents ofthe oxidized oil, thus providing rigidity and toughness in the cementstructure in spite of its substantial content of fluid non-hardeningconstituents. As a corollary the substantial proportion of fluidnon-hardening constituents in the cement requires the presence of asubstantial or major proportion of coagulated constituents to produce aneffective and practicable cement. Such function of the linoxyn isbelieved to be accomplished by occlusion of the constituents of FractionIII in the coagulated molecules of the linoxyn which, throughassociation, assume colloidal dimensions. Whether or not this is thecorrect theory, the fact remains that'to produce a satisfactory finishedlinoleum, it has always been found necessary to prepare the cementbinder in the form of a tough, rubbery, elastic-solid, requiring veryheavy machinery to handle and characterized by its poor or slow wettingproperties.

Our invention is based upon discoveries regarding the effect of varyingthe composition and mode of preparation of the oxidized oil component ofthe cement. Thus we have found that if a substantial proportion of theunoxidized and non-hardening constituents normally present in the oilbase of the cement, i. e., Fraction III, are eliminated, a linoleumcement of remark-able physical and chemical properties can be produced.Also, we have found that, coincident with such reduction in theproportion of these constituents, a highly satisfactory linoleum cementpossessing unexpected advantages can be prepared which is in fluidphase, by causing the cement to be substantially devoid of any linoxyncontent or to possess a substantially decreased ratio of linoxyn tothose fluid constituents of the oxidized oil which are capable ofhardening without further substantial oxidation. Such a modified cement,when admixed in the usual proportion with the common filler and pigmentmaterials, forms a linoleum composition that may be properly seasoned orcured in a fraction of the usual period and which, when seasoned,produces a finished linoleum having highly improved properties ashereinafter more fully described. Furthermore, such linoleum cement,being prepared in fluid phase rather than 1 as an elastic-solid, may beincorporated with the filler materials more thoroughly and in less timebecause of its high wetting properties and with but a fraction of theusual power requirements.

One embodiment of the process of our invention in the manufacture of theimproved linoleum or other mouldable compositions constituting theproduct of our invention comprises the steps of subjecting a substancewhich contains a drying or semi-drying oil, and which may contain aresinous material, to an oxidizing treatment limited substantially tothe formation of uncoagulated products of the oxidation, treating theoil to remove therefrom a substantial proportion of unoxidized andnon-hardening oil constituents, admixing the so prepared component ofoxidized oil with filler materials to form a mouldable composition,moulding the mix by pressure, and effecting partial conversion ofconstituents of the oxidized oil component into linoxyn, therebyproducing a sufficiently cured product, the effecting of such conversionbeing divided between the mixing, moulding, and curing steps in suchproportion as desired. Our product invention contemplates a finishedlinoleum or other composition of unusual flexibility and resistance tomoisture and soiling, comprising a binder in which the oil component ischaracterized by a substantially reduced ratio of unoxidized andnon-hardening oil constituents to all other constituents of the oilcomponent as compared with the ratio characterizing oil binders oflinoleum heretofore known.

In preparing the improved linoleum of our invention, we prefer to employlinseed oil as the oil base for the modified cement. Other drying orsemi-drying oils such as perilla oil, rubberseed oil, or soya bean oilmay be used, and in general any drying or semi-drying oil which, uponoxidation, yields a substantial amount of the oxidized glycerides oflinolic and/or linolenic acids in fluid phase will be foundsatisfactory. Also the mcdified cement of our improved linoleum shouldcont-ain a substantial proportion of resinous material. A wide choiceof? suitable resinous materials is available, among which may bementioned rosin, ester gum, fused congo, congo ester, kauri gum,paracoumarone resin; oil-soluble" or-oil-reactive synthetic resins ofthe phenol-aldehyde type, either'with or without rosin, etc. Forordinary purposes wood rosin will betfound most' desirable since it: isinexpensive; uniform' in quality, and easily soluble in the oil. Forspecial purposes; or to obtain special properties in the finishedlinoleum, other resins may prove more satisfactory. It will be foundpreferable to incorporate such resinous material with the oil base priorto the oxidation treatment. The presence of resin not only facilitatesthe: oxidation of the oil but markedly improves thetoughness of thefinal linoleum product. Alsotbysuchprocedure it becomes possible toincorporate with the oil component certain resins which could not:otherwise be incorporated such as paracoumarone; and certain glyptals,amberol, andtbakeliteresins having arelatively low acid value. Itshould. be pointed out that it is not necessary to incorporate theselectedresinous material with the. oil base prior to oxidation, as goodresults may also be obtained by first preparing the oxidized and treatedoil in the manner'hereinafter described and then adding thereto,preferably in solution, the-selected resin.

Byway of illustrating the various aspects of our process invention, wewill describe in detail a preferred embodiment thereof. Three parts oflinseed oil and one part of wood rosin, by weight, are heated in aWood-Bedford type of oxidizer to about 240 F. until the resin isdissolved. The temperature is. then lowered to about 180 F. and asuitable drier, for example, 04% cobalt linoleate, is added. The batch,at atemperature of approximately 180 F., 'is then blown with air orequivalent oxygen-containing gas for a period of 20 to hours. When atested sample just fails to completely dissolve in ethylether,the-oxidation is discontinued. The batch is then cooled and treated toeffect a separation of the unoxidized and non-hardening constituentsfromthe desired oxidized oil constituents. This separation may beeffected by subjecting the oxidized oil or oil-resin mix to selectiveextraction with a solvent capable of dissolving the undesirableconstituents but possessing littleif any solvating action upon theoxidized but uncoagulated constituents. which are desirablefor ourimproved linoleum-cement and which are fluid and are capable ofhardening without further substantial oxidation. The preferred solventis petroleum ether (boiling range 30 to'lfi C.), and" about 3 to 4volumes thereof to 1 volume of the oxidized oil or oil-resin mixshould-be employed. Petroleum naphtha (boiling range 60 to 160 0.) maybeused as an equivalent extracting solvent. Those oxidized butuncoagulated constituents of the oil or' oilresin mixture which aredesirable constituents for the linoleum cement, and a major portion ofthe resinous material form a lower layer, while substantial proportionsof the unoxidized and non-hardening oil constituents dissolve in theextracting solvent forming an upper layer. This upper layer is removedby decantation. The extraction process is preferably repeated two orthree times to assure an adequate separation. The remaining portion ofthe oxidized oil or oilresin mix, in fluid phase, is then subjected tolow heat, and preferably at reduced pressure, to remove the last.portion' of the extracting solvent, after whichit. isready for useas orin our improved linoleum cement. For convenience in handling, and toprevent premature solidification or gellation, the-desired constituentsof the oxidized oil or oil-resin mix, in fluid phase, obtained by theoxidizing-and separating treatment above described, are preferablydissolved in a suitable solvent such as toluol, butyl acetate, xylene,hiflash coal tar naphtha, etc., to provide a 60 to 80% solution. Wherethe resinous material. is incorporated with the oil component prior tothe oxidation treatment, this solution of the desired constituents ofthe oxidized and treated oil-resin mix constitutes the cement for ourimproved linoleum; Where the resinous material is not incorporated withthe oil base prior to the oxidizing treatment, the oxidation of the oilalone and the separation of the undesirable from the desirableconstituents of the oxidized products will be carried out in the samemanner as above described and to the solution of the separated desiredconstituents of the oxidized oil may be added theselected resinousmaterial. In either case, it will be found preferable to formulate thecement so that the non-volatile component thereof will compriseapproximately one part of resinous material to three parts of thedesired oxidized and separated oil constituents in fiuid phase. However,the addition of the resinous material is not critical to the realizationof many of the advantages of our invention, and it is within the purviewof the invention to omit the resinous material and to employ solely theprepared oil component in formulating the modified and improved cement,particularly where a softer composition may be desired.

It is to be noted that in the treatment of the raw oil or oil-resin mixto produce the cement, the oxidation is discontinued at, or just beforethe point where constituents of the oxidized oil have commenced tocoagulate to the gel or linoxyn phase. This point may be determined bythe ethyl ether test. So long as no linoxyn is formed, the constituentsof the batch undergoing oxidation willdissolve completely in ethylether, but upon the formation of linoxyn, a cloud-like precipitate willappear in the sample tested. Following the above described method, theyield of oxidized but uncoagulated constituents of the oil which are infiuid phase and are desirable ingredients of the linoleum cement, i. e.,that portion of the oxidized oil soluble in ethyl ether, but insolublein petroleum ether, varies from 60 to 75% by weight of the oil aftercompletion of the oxidizing treatment thereof. To a considerable extentthe yield depends upon the nature of the resin employed. A resin such asrosin, which is strongly acid in character, serves apparently as apeptizing agent to retard the coagulation of the oxidized constituentsof the oil, thus increasing the yield of these desired oxidizedconstituents in fluid phase. On the other hand, if no resin is employedor if a nearly neutral resin is selected, the yield will be lower. Whenemploying no resin, or a neutral or weakly acid resin, in thepreparation of the oil component of the cement, the percentage yield ofthe desired oxidized constituents of the oil may be somewhat increasedby adding to the oil or oil-resin mix prior to oxidation a smallamount-.1% to 2.0'%-of maleic acid (maleic acid anhydride) or equivalentacidic substance, difficultly volatile at the processing temperature.The maleic acid or maleic acid anhydride may be added in dry state butis more conveniently added in the form of. an acetone solution.

The desired oxidized oil constituents of the modified cement, which aresoluble in ethyl ether but insoluble in petroleum ether, comprisechiefly the oxidized glyceri-des of linolic and linolenic acids in fluidphase and uncoagulated. These constituents have the property ofcoagulating or hardening by conversion into linoxyn without substantialfurther oxidation and even without contact with air. The unoxidizedconstituents of the oil which are not oxidized in the oxidizingtreatment, which is so conducted as to produce the desired oxidizedconstituents in fluid phase, are either constituents of the oil whichcannot be oxidized by such treatment or by contact with air and do notpossess the property of hardening such as the glycerides of saturatedorganic acids of which stearic or palmitic are examples, or they areconstituents of the oil which are capable of being converted by theoxidizing treatment into substances having the property of hardening,but were not so converted, such as the glycerides of linolic andlinolenic acids. The other products of the oxidizing treatment which areundesirable as constituents of the modified cement, are those oxidizedoil constituents which do not possess the property of coagulating eventhough oxidized such as the oxidized glycerides of oleic acid. It isthese unoxidized and non-hardening constituents of the oil normallypresent after completion of the oxidizing treatment which are removed toa substantial extent by the separation treatment above described.

Although it is desirable that the amount of unoxidized and non-hardeningoil constituents, remaining in the linoleum cement as prepared, shouldbe at a minimum, nevertheless the difficulty and expense of securing incommercial operation a quantitative elimination of these constltuents,makes it inexpedient to attempt to obtain this end. As above pointedout, the advantages of this invention accrue from the elimination fromthe linoleum cement of a substantial proportion of the unoxidized andnon-hardening oil constituents of the oxidized drying or semi drying oilbase, thus making possible the preparation of an improved cement influid phase which contains little or no linoxyn. This aim may beaccomplished when the separation of the desirable and undesirableconstituents of the oxidized oil is carried to such an extent that theoil component of the cement contains approximately 93% or more ofoxidized but uncoagulated oil constituents soluble in ethyl ether butinsoluble in petroleum ether. Defining in another way the chemicalcharacter of the modified cement for producing our improved linoleum,the advantages of our invention may be realized if, in such cement, theratio of the unoxidized and non-hardening oil constituents, to all otheroil constituents of the cement, is 1 to 12 or more. By way ofcomparison, the corresponding ratio of these constituents in theconventional type of commercial linoleum cements heretofore known isalmost invariably 1 to 6 or less.

The next step in our improved process of manufacturing the products ofour invention is to combine with the modified cement prepared as abovedescribed, the requisite filler materials to form a mouldablecomposition. Normally the improved linoleum will comprise a proportionof vegetable fillers such as ground cork or wood flour and a proportionof mineral fillers such as whiting, china clay, asbestine, etc., as wellas pigments including both white pigments and the desired coloringpigments. The particular fillers and pigments and the proportions inwhich they may be employed are not essential features of our invention.In general we propose to employ any of the vegetable and mineral fillerswhich have been heretofore known or used in linoleum compositions and wepropose to employ such fillers in the amounts and proportions recognizedas standard practice. A generic formula may be stated as follows:

Modified cement 25% to 50% Vegetable fillers 25% to 35% Mineral fillersincluding pigments 25% to 40% Depending upon the nature of the productdesired, however, the proportion of the vegetable filler may beincreased above or decreased below the limits specified with acorresponding decrease or increase in the proportion of mineral fillersand pigments or one type of filler may be used to the exclusion of theother type.

A typical example, illustrating the formulation of our improved linoleumis as follows:350 pounds of an solution (in hi-flash naphtha) of the.oxidized and treated oil-resin cement prepared as above described isadmixed with 300 pounds of wood flour in a conventional type ofPfleiderer mixer, the mixer being warmed to drive off the solvent. Aftera preliminary mixing of the improved cement and wood flour, 200

pounds of whiting and 200 pounds of lithopone are then added and themixing is continued until the mass becomes thoroughly homogeneous andyields a smooth, strong sheet when calendered. The temperature of themix should usually be regulated so as not to exceed approximately F. andpreferably the mixing should be carried out, at least during its earlystages, at substantially lower temperatures. The period of mixing willbe determined by the type of linoleum to be made. Thus, composition tobe pressed or calendered directly onto a burlap or other base web, as inthe production of either the socalled moulded inlaid or the plainlinoleum, need be mixed only a few minutes whereas composition to beformed into unbacked sheets for cutting and inlaying will be mixed for alonger period in order that the freshly calendered sheet producedtherefrom may be tougher. The homogenized mix of fillers and cement isdumped from the mixer and disintegrated in any conventional manner as bypassing it through a german or scratcher or both, after which it isready for sheetirn, in accordance with standard practice.

One marked advantage of our invention is the ease with which themouldable composition may be prepared. Since the cement is incorporatedwhile in fluid phase, good wetting and dispersion thereof arefacilitated and much lighter mixing machinery may be used. The totaltime required for thoroughly mixing the several ingredients is reducedby 50% or more. Most important of all, the power required for efifeotingthe mixing of the fillers and binder may be as little as 10% of thatnormally required by the conventional methods now employed where thelinoleum cement is prepared and used in the form of a tough, rubberyelastic-solid. As above indicated, the temperature at which the mixingoperation is conducted and the period over which it is extended may varyin accordance with the character of the linoleum composition desired.Higher temperatures, i. e., temperatures of the order of 180 F., andlonger mixing periods will effect a limited conversion into linoxyn ofthe oxidized but fluid constituents of the oil component of the binderand the more extensive the formation of .linoxyn in this mixing stage,the tougher will be the resulting composition when calendered orsheeted. In general limited formation of linoxyn during the mixingoperation is desirable, but to facilitate thorough dispersion of thebinder and to effect incorporation of the fillers with a minimumexpenditure of power, such formation of linoxyn should be restrictedduring the early stages of the mixing. This regulation may be readilyaccomplished by control of the temperature of the mix, lowertemperatures being preferably employed during the early stages of themixing operation and higher temperatures being permitted only afterthorough dispersion of the fluid cement whereby the formation of anysubstantial proportion of linoxyn occurs only near the end of the mixingoperation.

The linoleum composition prepared as above described and sheeted,calendere-d, or otherwise moulded by pressure intothe desired form isfinally subjected to a seasoning treatment to effect a furtherconversion or solidification of the oxidized but uncoagulatedoilconstituents of the binder into linoxyn. This seasoning or curing ispreferably carried out at elevated temperatures, two to four days beingrequired at a temperature of 170 F. Linoleum of our invention mayhowever be seasoned at lower temperatures or at temperatures as high as200 to 210 F. in which latter case the seasoning period will beshortened to about 24 hours. By Way of contrast, linoleum compositionprepared according to the process h heretofore known and use-d, requiresa seasoning period varying from 7 to 40 days at a temperature of 1'70 to180 F. and in the heavier gauges cannot successfully be seasoned abovethis temperature without formation of a so-called wet seam, that is, asheet having a hard surface and a soft center. The importance of thissubstantial reduction in seasoning period will be apparent to thoseskilled in the art.

The improved linoleum of our invention resulting from the process justdescribed is characterized by markedly improved flexibility, suchsuperior flexibility being present not only when the linoleum is freshlymanufactured but continuing indefinitely as the product ages. Thischaracteristic is attributable to the substantial reduction in theproportion of the unoxidized and non-hardening constituents of the oilcomponent of the cement which constituents have no binding power inthemselves but when present are strongly adsorbed into the capillarystructure of the linoxyn formed during the seasoning treatment andsubsequent aging so that such linoxyn behaves like a rigid solid. Ourimproved linoleum also exhibits substantially increased resistance tosoiling and to moisture. This is attributable to the very thoroughwetting of each particle of the vegetable filler material obtainable byincorporating the oxidized oil binder in the form of a fluid instead ofan elastic-solid. The particles of vegetable filler thus becomeimpregnated and coated with the cement and are thereby rendered highlywater-resistant. Furthermore, as will be noted in the description of theprocess, the mineral fillers and pigments are preferably added after thevegetable fillers have been pre-mixed with the cement, this sequence ofoperations permitting each particle of the vegetable filler first to becovered with cement and such cement-covered particles then tobecomecoated with mineral fillers thereby greatly improving theresistance of the linoleum to soiling or traflic while preserving theresiliency for which linoleum as a product is renowned.

According to the conventional method, above referred to, of chemicallyevaluating linoleum and 5 linoleum cements, our improved linoleumproduct is characterized by a substantially decreased ratio ofunoxidized and non-hardening constituents (i. e., Fraction III) of theoxidized oil component of the binder to those oil constituents of thebinder present in the form of linoxyn and in the form of oxidized butuncoagulated pro-ducts of oxidation. In linoleum prepared according toconventional processes heretofore known or used, about 26% of theunoxidized constituents of the oil component of the cement are convertedinto oxidized or oxidized and coagulated constituents during theseasoning treatment. This conversion also continues, though at a slowrate, as the linoleum ages. Thus, as compared with the 15% to 40% ofunoxidized and non-hardening constituents (i. e., Fraction III) normallypresent in the oil component of the conventional type of linoleum cementbefore seasoning, the percentage in such linoleum cement may be reducedto 12% to after seasoning of the linoleum and 10% to 25% after years ofaging. Expressed in another way the ratio of these constituents to theremainder of the constituents of the oil component of the binder ofccnven- 30 tional linoleum is normally at least 1 to 7 after seasoningand normally at least 1 to 9 even after long aging. In contrast to thesepercentages and ratios, our improved linoleum after the seasoningtreatment comprises a. binder or cement wherein the unoxidized andnon-hardening constituents of the oil component, i. e.constituentssoluble in petroleum ether-are but approximately 6% or less of the totaloil component of the cement and the ratio of such undesirableconstituents to the remainder of the constituents of the oil componentis less than 1 to 15, normally about 1 to 20.

It will be apparent to those skilled in the art that this inventionconstitutes a major advance in the linoleum industry. It will also beclear that the teachings of the improved composition or linoleum productand of the various steps in the method of producing such composition orproduct as set forth herein may be applied in many ways to secure one ormore of the enumerated or recognized advantages, or may be modified indifferent aspects without departing from the spirit of the invention.Thus, for example, the improved binder or cement of our invention may beemployed in conjunction with other binders, as, for example,nitrocellulose, chlorinated rubber, or the like in preparing moul-dablecompositions or cements therefrom, such composite cements or binderspossessing those advantages accuring from the presence therein of an oilcomponent prepared in accordance with our invention. The severalfeatures of this invention cooperate in such manner, when they are allused in conjunction, as to produce results that are due to suchcooperation and are additional to such results'as flow from the separateuse of those features or from .a use of those features in such mannerthat they are not properly coordinated; and in the best practice of ourinvention, all of the features above described, or equivalent features,will preferably be employed in the cooperative relation above described,or equivalent relation. However, certain of those features, such as thereduced content of non-hardening and unoxidized constituents of theoxidized oil prodnot to which fillers, etc., are added, and also thefluidity of the material to which fillers, etc., are added, used eithersingly or in the absence of one or more of the several featuresdescribed, produce novel and advantageous results when so used, and suchuse falls within the spirit of our invention. It is to these fundamentalteachings as set forth in the foregoing specification herein that theinventors assert their pioneership.

We claim:

1. The process which comprises the steps of subjecting a drying orsemi-drying oil to an oxidizing treatment, discontinuing the oxidizingtreatment prior to substantial coagulation of the oxidized oil, treatingthe products of oxidation to remove therefrom a substantial proportionof unoxidized oil constituents and nonhardening oil constituents,admixing filler material with the remaining fluid oxidized oilconstituents to form a mouldable composition, moulding the mix bypressure, and subjecting the moulded mixture to treatment for convertingoxidized oil constituents therein into linoxyn.

2. The process which comprises the steps of admixing a drying orsemi-drying oil and resinous material, subjecting the mixture to anoxidizing treatment, discontinuing the oxidizing treatment prior tosubstantial coagulation of oxidized oil constituents to form linoxyn,treating the products of oxidation to remove therefrom a substantialproportion of the constituents of the oil which are unoxidized ornon-hardening, admixing filler material with the remaining fluidoxidized oil-resin binder to form a mouldable composition, moulding themix by pressure, and subjecting the moulded mixture to treatment forconverting oxidized oil constituents therein into linoxyn.

3. The process which comprises the steps of subjecting a drying orsemi-drying oil to an oxidizing treatment, discontinuing the oxidizingtreatment prior to substantial coagulation of oxidized oil constituentsto form linoxyn, treating the products of oxidation to remove therefroma substantial proportion of the unoxidized oil constituents andnon-hardening oil constituents, combining with the fluid oxidized oilconstituents a resinous material, admixing filler material with theprepared oxidized oil-resin binder to form a mouldable composition,moulding the mix by pressure, and subjecting the moulded mixture totreatment for converting oxidized oil constituents therein into linoxyn.

4. The process which comprises the steps of subjecting a substancecomprising a drying or semi-drying oil to an oxidizing treatment limitedsubstantially to formation of uncogulated products of oxidation,selectively extracting from the products of oxidation the unoxidized andnon-hardening constituents of the oil, combining the remaining fluidoxidized constituents of the oil with filler material to form amouldable composition, moulding the mix by pressure, and subjecting themoulded mixture to treatment for converting oxidized oil constituentstherein into linoxyn.

5. The process which comprises the steps of subjecting a substancecomprising a drying or semi-drying oil to oxidizing treatment limitedsubstantially to the formation of uncogulated products of oxidation,selectively extracting the resulting product with a low boiling liquidhydrocarbon to remove unoxidized and non-hardening oil constituents,admixing filler material with the remaining fluid oxidized oilconstituents to form a mouldable composition, moulding the mix bypressure, and subjecting the moulded product to the action of anelevated temperature to effect conversion of oxidized oil constituentsinto linoxyn.

6. The process which comprises the steps of subjecting a substancecomprising a drying or semi-drying oil and an acidic resin to oxidizingtreatment limited substantially to the formation of uncoagulatedproducts of oxidation, extracting the resulting product with low boilingliquid hydro-carbon to remove unoxidized and nonhardening oilconstituents, admixing the remaining fluid oxidized oil constituentswith filler material to form a mouldable composition, moulding the mixby pressure, and seasoning.

'7. The process which comprises the steps of subjecting a, substancecomprising a drying or semi-drying oil to oxidation treatment limitedsubstantially to the formation of uncoagulated products of oxidation,treating the product to remove therefrom the unoxidized andnon-hardening oil constituents, combining the fluid oxidized oilconstituents with 50% or more of vegetable and/or mineral fillers toform a mouldable composition, moulding the composition, and seasoning.

8. The process which comprises the steps of subjecting a substancecomprising a resinous material and a drying or semi-drying oil to anoxidizing treatment limited substantially to the formation ofuncoagulated products of oxidation, treating the oxidation products toremove therefrom a substantial proportion of the non-hardeningconstitutents thereof, combining the remaining fluid oxidized oil-resinconstituents with 50% or more of vegetable and/or mineral fillers toform a mouldable composition, moulding the composition into the desiredform, and subjecting the moulded product to heat to convert oxidized oilconstituents therein into linoxyn.

9. The process which comprises the steps of subjecting a substancecomprising a drying or semi-drying oil to an oxidizing treatment limitedsubstantially to the formation of uncoagulated products of oxidation,treating the product to remove therefrom unoxidized and non-hardeningoil constituents, premixing the remaining fluid oxidized oilconstituents with a vegetable filler, adding mineral fillers to thepremix to form a mouldable composition, moulding the composition bypressure, and effecting conversion of oxidized oil constituents thereininto linoxyn.

10. The process which comprises the steps of subjecting a substancecomprising a resinous material and a drying or semi-drying oil to anoxidizing treatment limited substantially to the formation ofuncoagulated products of oxidation, treating the product to removetherefrom a substantial proportion of the non-hardening constituentsthereof, premixing the remaining fluid oxidized oil-resin constituentswith a vegetable filler, adding mineral fillers to the premix to form amouldable composition, moulding the composition into the desired form,and effecting conversion of oxidized oil constituents therein intolinoxyn.

11. The process which comprises the steps of subjecting a substancecomprising a drying or semi-drying oil to an oxidizing treatment limitedsubstantially to the formation of uncoagulated products of oxidation,separating the product into a fraction which is richer than said productin fluid oxidized oil constituents, and capable of hardening withoutfurther substantial oxidation, and a fraction which is richer than saidproduct in unoxidized and non-hardening oil constituents, admixingfiller material with the first named fraction to form a mouldablecomposition, moulding by pressure, and seasoning.

12. The process which comprises the steps of subjecting a substancecomprising a resinous material and a drying or semi-drying oil to anoxidizing treatment limited substantially to the formation ofuncoagulated products of oxidation, separating the product into afraction which is richer than said product in fluid oxidized oilconstituents, and capable of hardening without further substantialoxidation, and a fraction which is richer than said product inunoxidized and non-hardening oil constituents, admixing the first namedfraction with filler material to form a mouldable composition, mouldingby pressure, and seasoning.

13. In a process for producing a composition comprising constituents ofoxidized drying or semi-drying oil, the steps comprising subjecting adrying or semi-drying oil to an oxidizing treatment, treating theproducts of oxidation to re move therefrom a substantial proportion ofunoxidized oil constituents and non-hardening oil constituents, admixingfiller material with the remaining fluid oxidized oil constituents toform a mouldable composition, moulding the mix by pressure, andsubjecting the moulded mixture to treatment for converting oxidized oilconstituents therein into linoxyn.

14. In a process for producing a composition I comprising constituentsof oxidized drying or semi-drying oil, the steps comprising subjecting adrying or semi-drying oil to an oxidizing treatment, discontinuing theoxidizing treatment prior to substantial coagulation of the oxidizedoil, treating the products of oxidation to remove therefrom asubstantial proportion of unoxidized oil constituents and non-hardeningoil constituents, dissolving the remaining fluid oxidized oilconstituents in a suitable solvent, admixing filler material with suchsolution to form a mouldable composition, and moulding said composition.

15. Linoleum or similar composition composed of filler mamrial and abinder comprising the hardened component of oxidized drying orsemidrying oil which, after oxidation of the oil is in fluid phase, isseparated from a substantial proportion of unoxidized and non-hardeningoil constituents, of the oxidized oil, and is capable of hardeningwithout further substantial oxidation.

16. Linoleum or similar composition composed of filler material and abinder comprising a resinous substance and the hardened component ofoxidized drying or semi-drying oil which, after oxidation of the oil isin fluid phase, is separated from a substantial proportion of unoxidizedand non-hardening oil constituents of the oxidized oil, and is capableof hardening without further substantial oxidation.

17. Linoleum or similar composition composed of vegetable and/or mineralfillers and 25% to 50% of a binder comprising the hardened component ofoxidized drying or semi-drying oil which, after oxidation of the oil isin fluid phase, is separated from a substantial proportion ofnonhardening oil constitutents of the oxidized oil, and is capable ofhardening without further substantial oxidation.

18. A mouldable composition comprising filler material and a bindercomprising the fluid component of oxidized drying or semi-drying oilwhich is capable of hardening without further substantial oxidation, andis separated from a substantial proportion of unoxidized andnon-hardening oil constituents of the oxidized oil, and suflicientsolvent for said fluid component to maintain its fluidity.

19. A mouldable composition comprising filler material and a bindercomprising a resinous substance and the fluid component of oxidized dry-10 ing or semi-drying oil which is separated from a substantialproportion of unoxidized and nonhardening oil constituents of theoxidized oil, and is capable of hardening without further substantialoxidation, and sufficient solvent for said fluid component to maintainits fluidity.

20. A mouldable composition composed of 50% to 75% of filler material, abinder comprising that fluid component of oxidized drying or semi-dryingoil which is capable of hardening without further substantial oxidationand is separated from a substantial proportion of unoxidized andnon-hardening oil constituents of the oxidized oil, and sufficientsolvent for said fluid component to maintain its fluidity.

21. Linoleum or similar composition composed of filler material and abinder comprising the hardened component of oxidized drying orsemidrying oil which, after oxidation of the oil is in fluid phase, iscapable of hardening without further substantial oxidation, and hasassociated with it less than 6% of oil constituents soluble in petroleumether.

22. Linoleum or similar composition composed of 50% to 75% of fillermaterial and 25% to 50% of a binder comprising the hardened component ofoxidized drying or semi-drying oil which, after oxidation of the oil isin fluid phase, is capable of hardening without further substantialoxidation, and which binder has associated with it less than 6% ofunoxidized and non-hardening oil constituents of the oxidized oilsoluble in petroleum ether.

23. The process which comprises the steps of subjecting a drying orsemi-drying oil to an oxidizing treatment, discontinuing the oxidizingtreatment prior to substantial coagulation of the oxidized oil, treatingthe products of oxidation to remove therefrom a substantial proportionof unoxidized oil constituents and non-hardening oil constituents,admixing filler material with the remaining fluid oxidized oilconstituents to form a mouldable composition, treating the mixture toeffect partial conversion of oxidized constituents therein into linoxyn,thereafter moulding the mix by pressure, and subjecting the mouldedmixture to treatment for converting oxidized oil constituents thereininto linoxyn.

24. The process which comprises the steps of subjecting a drying orsemi-drying oil to an oxidizing treatment, discontinuing the oxidizingtreatment prior to substantial coagulation of the oxidized oil, treatingthe products of oxidation to remove therefrom a substantial proportionof unoxidized oil constituents and non-hardening oil 5 constituents,admixing filler material with the remaining fluid oxidized oilconstituents to form a mouldable composition, prolonging the mixing atelevated temperature, thereafter moulding the mix by pressure, andsubjecting the moulded 70 mixture to treatment for converting oxidizedoil constituents therein into linoxyn.

ROBERT D. BONNEY.

WALTER S. EGGE.

